Diastereotopic group selective reactions have considerable utility in asymmetric synthesis. Investigations toward novel applications of this technique will expose further opportunities for reaction stereocontrol. Recent developments in metalmediated C-H bond oxidation have led to a Rh(II)-catalyzed, C-H amination strategy en route to functionalized amine derivatives with varied structural profiles. This unique transformation could potentially be employed in a group selective process. With this in mind, the major objectives of the following proposal are: (i) to develop substrate- and reagent-controlled, Rh(II)-catalyzed, group selective C-H amination methods; (ii) to explore inter- and intramolecular additions to the resultant oxathiazinane N,O-acetals; and (iii) to demonstrate the utility of diastereotopic group selective C-H amination in the stereoselective synthesis of the recently isolated iboga alkaloid 19(S)-hydroxyibogamine. The iboga family of alkaloids contains numerous members, most notable of which is the potent central nervous system stimulant (-)-ibogaine. Other members of the iboga family exhibit various pharmacological profiles, from oral contraceptive to cytotoxic activities. Coupled with their intriguing structural motifs, the broad range of biological activity displayed by the iboga alkaloids makes them attractive targets for synthesis, and new approaches toward these compounds are warranted.